Method for improving crystallization quality of perovskite thin film
By preparing a smooth buried interface through atomic layer deposition and adding NSH to regulate perovskite nucleation and crystallization, the problem of imperfect perovskite crystallization was solved, thus improving the photoelectric conversion efficiency of perovskite solar cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANCHANG UNIV
- Filing Date
- 2026-01-12
- Publication Date
- 2026-05-05
AI Technical Summary
In existing technologies, the perovskite crystallization process of perovskite solar cells is affected by the roughness of the buried interface, resulting in imperfect crystallization and pore defects, which affect device performance.
A smooth buried interface was prepared using atomic layer deposition (ALD) technology, and N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride (NSH) was added to the perovskite precursor to regulate the nucleation and crystallization process of perovskite through the synergistic effect of the interface and the bulk.
It improves the crystal quality of perovskite thin films and enhances the photoelectric conversion efficiency and performance of devices, including improvements in open-circuit voltage, short-circuit current density, and fill factor.
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Figure CN121985705A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of solar cell technology, specifically relating to a method for improving the crystallization quality of perovskite thin films. Background Technology
[0002] Perovskite solar cells, as a novel photovoltaic technology with advantages such as low energy consumption, low cost, abundant raw material sources, and simple fabrication processes, have attracted widespread attention and research. Currently, the photoelectric conversion efficiency of these cells continues to improve, and significant breakthroughs have been achieved in large-scale fabrication technology.
[0003] In the fabrication of perovskite solar cells, spin-coated alumina is widely used to modify the interface. Its primary function is to improve the wettability of the charge transport layer (such as MeO-2PACz) to facilitate the spreading of the perovskite precursor solution; secondly, it can fill the voids in the MeO-2PACz layer. However, the alumina used in this method is usually in the form of nanoparticles, which have an inherent tendency to agglomerate. This agglomeration significantly increases the roughness of the interface, which in turn negatively affects the subsequent crystallization process of the perovskite layer, leading to defects such as incomplete crystallization and voids at the buried interface, ultimately impairing device performance.
[0004] Perovskite crystallization is a complex, non-equilibrium process that begins at the buried interface and extends into the film bulk. Therefore, the crystallization process is influenced by both the bulk material and the buried interface. Current techniques, such as altering the buried material or adding passivating agents to the perovskite precursor, cannot effectively control the crystallization process. Therefore, there is an urgent need to develop a new method to improve the crystallization quality of perovskite films and address these issues. Summary of the Invention
[0005] To address the problems mentioned in the background section, the present invention aims to provide a method for improving the crystallinity quality of perovskite thin films. The present invention utilizes atomic layer deposition (ALD) technology to prepare a smooth buried interface and adds N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride to the perovskite precursor. The interface and the bulk work synergistically to jointly regulate the nucleation and crystallization process of the perovskite.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: On one hand, the present invention provides a method for improving the crystallinity quality of perovskite thin films, comprising the following steps:
[0007] The buried interface was prepared by atomic layer deposition;
[0008] N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride (NSH) was added to the perovskite precursor solution to obtain a perovskite precursor solution containing N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride. The perovskite precursor solution containing N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride was deposited on the buried interface to obtain a perovskite film.
[0009] The buried interface is an alumina film, tin oxide film, zinc oxide film, indium oxide film, or titanium oxide film.
[0010] The pulse duration of the metal source in the atomic layer deposition is 0.01-0.02 s, and the pulse duration of the oxide source in the atomic layer deposition is 0.001-1 s.
[0011] The buried interface prepared using the pulse time specified in this invention can achieve ideal wettability, thereby ensuring a suitable number of nucleation sites for perovskite and improving the crystallization quality of perovskite. In this invention, N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride is added to the perovskite precursor solution, which allows the oxygen atoms in the sulfonamide of N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride to coordinate with aluminum, tin, zinc, indium, or titanium ions, thus synergistically regulating perovskite crystallization from both bulk and interfacial perspectives.
[0012] Furthermore, the metal source used for the atomic layer deposition is an aluminum source, a tin source, a zinc source, an indium source, or a titanium source;
[0013] The aluminum source is trimethylaluminum or triisobutylaluminum;
[0014] The tin source is tetrakis(dimethylamino)tin;
[0015] The zinc source is diethylzinc;
[0016] The indium source is trimethylindium;
[0017] The titanium source is tetrakis(dimethylamino)titanium.
[0018] Furthermore, the oxidation source used for the atomic layer deposition is water, ozone, or hydrogen peroxide.
[0019] Furthermore, the thickness of the buried interface is 0.3-8 Å.
[0020] Furthermore, the perovskite precursor solution is 1.5 mol / L FA. 0.814 MA 0.136 Cs 0.05 Pb(I 0.923 Br 0.045 Cl 0.032 )3 solution.
[0021] Furthermore, the ratio between the perovskite precursor solution and N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride is 1 mL: (0.2-0.5 mg).
[0022] On the other hand, the present invention provides a perovskite thin film prepared by any of the methods described above for improving the crystallinity quality of perovskite thin films.
[0023] On the other hand, the present invention provides an application of the above-described perovskite thin film in perovskite devices.
[0024] In another aspect, the present invention provides a perovskite device comprising the perovskite thin film described above.
[0025] Further, it sequentially includes an indium tin oxide glass layer, a [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid film, the aforementioned perovskite film, a phenylethylamine iodide film, and a [6,6]-phenyl C 61 Methyl butyrate film, copper bath film, silver electrode.
[0026] Compared with the prior art, the present invention has the following beneficial effects:
[0027] 1) The buried interface prepared by atomic layer deposition in this invention can achieve nanometer-level precision film deposition and obtain a uniform interface layer, laying an ideal foundation for the growth of high-quality perovskite films.
[0028] 2) This invention prepares a buried interface through atomic layer deposition and changes the pulse time to change the surface wettability, thereby adjusting the nucleation sites to improve the crystallization quality;
[0029] 3) Adding N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride to the perovskite precursor solution increases the size of the perovskite precursor micelles, which synergistically improves the crystallization quality of perovskite with the atomic layer deposition (ALD) interface. Attached Figure Description
[0030] Figure 1 This is a schematic diagram of the buried interface prepared by atomic layer deposition in this invention;
[0031] Figure 2 This is a schematic diagram of the spin-coating preparation of thin films according to the present invention;
[0032] Figure 3 In Figure 'a', the contact angle test result of the buried interface prepared in Comparative Example 2 of this invention is shown. Figure 3 In the figure, b represents the contact angle test result of the buried interface prepared in Example 1 of the present invention. Figure 3 In the figure, c represents the contact angle test result of the buried interface prepared in Comparative Example 1 of this invention;
[0033] Figure 4 The image shows the dynamic light scattering test results of the perovskite precursor solution and the perovskite precursor solution containing NSH in Example 1 of this invention.
[0034] Figure 5 In the figure, 'a' is a scanning electron microscope image of the perovskite thin film prepared in Comparative Example 2 of this invention. Figure 5 In the figure, b is a scanning electron microscope image of the perovskite thin film prepared in Comparative Example 3 of this invention. Figure 5 c in the figure is a scanning electron microscope image of the perovskite thin film prepared in Example 1 of the present invention;
[0035] Figure 6 The perovskite devices prepared in Example 2, Comparative Example 4, and Comparative Example 5 are shown as current-voltage curves. Detailed Implementation
[0036] To better understand the content of this invention, the following detailed description is provided in conjunction with specific implementation methods. However, the scope of protection of this invention is not limited to the following embodiments.
[0037] Example 1
[0038] Preparation of the buried interface: This was performed in an atomic layer deposition (ALD) apparatus at a chamber temperature of 80°C. A uniform alumina film with a thickness of approximately 0.46 Å was grown on the substrate in two cycles. The metal source was trimethylaluminum, and the oxide source was water; the pulse time for water was 0.1 s, and the pulse time for trimethylaluminum was 0.015 s. A schematic diagram of the ALD preparation of the buried interface is shown below. Figure 1 As shown.
[0039] Preparation of perovskite thin films: in 1.5 mol / L FA 0.814 MA 0.136 Cs 0.05 Pb(I 0.923 Br 0.045 Cl 0.032 N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride (NSH) was added to solution 3 to obtain a perovskite precursor solution containing NSH. The solubility of N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride was 0.3 mg / mL. The perovskite precursor solution containing NSH was spin-coated onto the buried interface in a glove box to obtain a perovskite film (including the buried interface). A schematic diagram of the spin-coating preparation of the film is shown below. Figure 2 As shown.
[0040] Example 2
[0041] Fabrication of perovskite devices: An indium tin oxide transparent electrode was deposited on a glass surface to obtain an indium tin oxide glass layer. Further deposition of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) followed by the preparation of a perovskite thin film (using the same method as in Example 1). Subsequently, phenylethylamine iodide (PEAI) was spread, followed by the preparation of [6,6]-phenylC 61 methyl butyrate film (PC) 61 The process begins with atomic layer deposition (BM), followed by the preparation of a copper bath thin film (BCP). Finally, a silver electrode (Ag) is deposited using a metal evaporation process to achieve complete perovskite device fabrication. Except for the alumina thin film, which is prepared in an atomic layer deposition apparatus and the silver electrode, which is prepared in an evaporation apparatus, all other layers are prepared by spin coating in a glove box. A schematic diagram of the spin coating preparation is shown below. Figure 2 As shown.
[0042] Comparative Example 1
[0043] Preparation of the buried interface: This was performed in an atomic layer deposition (ALD) apparatus at a chamber temperature of 80°C. A uniform alumina film with a thickness of approximately 2.7 Å was grown on the substrate through two cycles. The metal source was trimethylaluminum, and the oxide source was water; the pulse time for water was 0.1 s, and the pulse time for trimethylaluminum was 0.03 s. A schematic diagram of the ALD preparation of the buried interface is shown below. Figure 1 As shown.
[0044] Comparative Example 2
[0045] Preparation of the embedded interface: Alumina was spin-coated at a speed of 4000 r / min and an acceleration of 2000 r / s. 2 Spin coating time: 30 seconds.
[0046] Preparation of perovskite thin films: 1.5 mol / L FA... 0.814 MA 0.136 Cs 0.05 Pb(I 0.923 Br 0.045 Cl 0.032 Solution 3 is spin-coated onto the buried interface inside a glove box to obtain a perovskite thin film (including the buried interface). A schematic diagram of the spin-coating thin film preparation is shown below. Figure 2 As shown.
[0047] Comparative Example 3
[0048] Preparation of the buried interface: This was performed in an atomic layer deposition (ALD) apparatus at a chamber temperature of 80°C. A uniform alumina film with a thickness of approximately 0.46 Å was grown on the substrate in two cycles. The metal source was trimethylaluminum, and the oxide source was water; the pulse time for water was 0.1 s, and the pulse time for trimethylaluminum was 0.015 s. A schematic diagram of the ALD preparation of the buried interface is shown below. Figure 1As shown.
[0049] Preparation of perovskite thin films: 1.5 mol / L FA... 0.814 MA 0.136 Cs 0.05 Pb(I 0.923 Br 0.045 Cl 0.032 Solution 3 is spin-coated onto the buried interface inside a glove box to obtain a perovskite thin film (including the buried interface). A schematic diagram of the spin-coating thin film preparation is shown below. Figure 2 As shown.
[0050] Comparative Example 4
[0051] Fabrication of perovskite devices: An indium tin oxide transparent electrode was deposited on a glass surface to obtain an indium tin oxide glass layer. [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid was then deposited, followed by the preparation of a perovskite thin film (using the same method as in Comparative Example 2). Subsequently, phenylethylamine iodide was spread, and then [6,6]-phenylC 61 A methyl butyrate film was first prepared, followed by a copper bath film, and finally, a silver electrode was deposited using a metal evaporation process to achieve the complete fabrication of the perovskite device. Except for the silver electrode, which was deposited in an evaporation apparatus, all other layers were prepared by spin coating in a glove box.
[0052] Comparative Example 5
[0053] Fabrication of perovskite devices: An indium tin oxide transparent electrode was deposited on a glass surface to obtain an indium tin oxide glass layer. [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid was then deposited, followed by the preparation of a perovskite thin film (using the same method as in Comparative Example 3). Subsequently, phenylethylamine iodide was spread, and then [6,6]-phenylC 61 A methyl butyrate film was prepared, followed by a copper bath film, and finally, a silver electrode was deposited using a metal evaporation process to achieve the complete fabrication of the perovskite device. Except for the alumina film, which was prepared in an atomic layer deposition apparatus and the silver electrode, which was prepared in an evaporation apparatus, all other layers were prepared by spin coating in a glove box.
[0054] Contact angle tests were performed on the buried interfaces prepared in Example 1, Comparative Example 1, and Comparative Example 2, respectively. This was achieved by adding a perovskite precursor solution to the buried interfaces. The results are as follows: Figure 3 As shown. From Figure 3As can be seen, the contact angle of trimethylaluminum is 10.8° when the pulse time is 0.015s. Changing the pulse time to 0.03s increases the contact angle to 25.7°-26.0°, while the contact angle of spin-coated alumina is 21.8°-22.0°. Changing the pulse time alters the wettability of the substrate interface. At a pulse time of 0.015s, the wettability is improved compared to spin-coated alumina, which is beneficial for the uniform deposition of the perovskite precursor solution and reduces microscopic defects.
[0055] Dynamic light scattering tests were performed on the perovskite precursor solution from Example 1 and the perovskite precursor solution containing NSH, respectively. The results are as follows: Figure 4 As shown. From Figure 4 As can be seen, there is a strong interaction between NSH and the components in the perovskite precursor solution, which increases the size of the perovskite precursor micelles from 560 nm to 2600 nm, thereby improving the perovskite grain size.
[0056] Scanning electron microscopy was performed on the perovskite films prepared in Example 1, Comparative Example 2, and Comparative Example 3, respectively. The results are as follows: Figure 5 As shown. From Figure 5 As can be seen, the change in the wettability of the buried interface and the increase in the size of the perovskite precursor micelles lead to the increase in perovskite grain size, which improves the crystallinity.
[0057] The perovskite devices prepared in Example 2, Comparative Example 4, and Comparative Example 5 were subjected to current-voltage curve testing, and the effective area was 0.09 cm². 2 The result is as follows Figure 6 As shown in the table below.
[0058]
[0059] from Figure 6 As can be seen from the data in the table, the overall performance of the device was improved after atomic layer deposition and NSH bulk doping. Compared with the perovskite device prepared in Comparative Example 4, the open-circuit voltage of the perovskite device prepared in Example 2 increased from 1.146V to 1.160V, and the short-circuit current density increased from 22.23mA / cm². 2 Increased to 25.21 mA / cm 2 The fill factor increased from 80.39% to 83.32%, and the overall device efficiency increased from 21.44% to 25.49%. The improvement in device performance is inseparable from the improvement in the crystal quality of the perovskite thin film.
[0060] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several modifications and improvements can be made without departing from the inventive concept, and these all fall within the protection scope of the present invention.
Claims
1. A method for improving the crystallinity quality of perovskite thin films, characterized in that, Includes the following steps: The buried interface was prepared by atomic layer deposition; N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride was added to the perovskite precursor solution to obtain a perovskite precursor solution containing N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride. The perovskite precursor solution containing N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride was deposited on the buried interface to obtain a perovskite film. The buried interface is an alumina film, tin oxide film, zinc oxide film, indium oxide film, or titanium oxide film. The pulse duration of the metal source in the atomic layer deposition is 0.01-0.02 s, and the pulse duration of the oxide source in the atomic layer deposition is 0.001 s-1 s.
2. The method for improving the crystallinity quality of perovskite thin films according to claim 1, characterized in that, The metal source used for atomic layer deposition is an aluminum source, a tin source, a zinc source, an indium source, or a titanium source; The aluminum source is trimethylaluminum or triisobutylaluminum; The tin source is tetrakis(dimethylamino)tin; The zinc source is diethylzinc; The indium source is trimethylindium; The titanium source is tetrakis(dimethylamino)titanium.
3. The method for improving the crystallinity quality of perovskite thin films according to claim 1, characterized in that, The oxidation source used in the atomic layer deposition is water, ozone, or hydrogen peroxide.
4. The method for improving the crystallinity quality of perovskite thin films according to claim 1, characterized in that, The thickness of the buried interface is 0.3-8 Å.
5. The method for improving the crystallinity quality of perovskite thin films according to claim 1, characterized in that, The perovskite precursor solution is 1.5 mol / L FA. 0.814 MA 0.136 Cs 0.05 Pb(I 0.923 Br 0.045 Cl 0.032 )3 solution.
6. The method for improving the crystallinity quality of perovskite thin films according to claim 1, characterized in that, The ratio between the perovskite precursor solution and N-(6-aminohexyl)-1-naphthalenesulfonamide hydrochloride is 1 mL: (0.2-0.5 mg).
7. A perovskite thin film, characterized in that, It is prepared by the method for improving the crystallinity quality of perovskite thin films as described in any one of claims 1-6.
8. The application of the perovskite thin film according to claim 7 in perovskite devices.
9. A perovskite device, characterized in that, Includes the perovskite thin film as described in claim 7.
10. The perovskite device according to claim 9, characterized in that, The film comprises, in sequence, an indium tin oxide glass layer, a [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid film, the perovskite film of claim 7, a phenylethylamine iodide film, and [6,6]-phenylC 61 Methyl butyrate film, copper bath film, silver electrode.